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CN-121991476-A - Medical thermoplastic polycaprolactone composite material and preparation method and application thereof

CN121991476ACN 121991476 ACN121991476 ACN 121991476ACN-121991476-A

Abstract

The invention discloses a medical thermoplastic polycaprolactone composite material, and a preparation method and application thereof. The medical thermoplastic polycaprolactone composite material comprises an inner layer material and at least one outer layer material, wherein the inner layer material is a core layer comprising fiber bundles, first polycaprolactone resin and a first auxiliary agent, the at least one outer layer material wraps the core layer and comprises second polycaprolactone resin, glass beads and a second auxiliary agent, the fiber bundles continuously extend from one end of the core layer to the opposite end of the core layer, and at least the second auxiliary agent of the first auxiliary agent and the second auxiliary agent comprises a VOC inhibitor. The composite material disclosed by the invention is based on a multi-component material system design, so that the effect of performance synergy among all components can be achieved, the mechanical property of the material is obviously improved, and meanwhile, the odor performance, the anti-adhesion performance and the shrinkage performance are excellent.

Inventors

  • KANG PENG
  • CAI TAO
  • XIN QI
  • XU KAI
  • GAO DALI
  • SHI SHENGPENG

Assignees

  • 中国石油化工股份有限公司
  • 中石化(北京)化工研究院有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (12)

  1. 1. A medical thermoplastic polycaprolactone composite, wherein the medical thermoplastic polycaprolactone composite comprises an inner layer material and at least one outer layer material, the inner layer material is a core layer comprising fiber bundles, a first polycaprolactone resin and a first aid, the at least one outer layer material encapsulates the core layer and comprises a second polycaprolactone resin, glass beads and a second aid, wherein the fiber bundles extend continuously from one end of the core layer to an opposite end thereof, and at least the second aid of the first aid and the second aid comprises a VOC inhibitor.
  2. 2. The medical thermoplastic polycaprolactone composite according to claim 1, wherein the amount of the first polycaprolactone resin is 15-90 parts by weight, preferably 20-70 parts by weight, more preferably 40-70 parts by weight, still more preferably 50-70 parts by weight, and the amount of the fiber bundles is 10-85 parts by weight, 20-70 parts by weight, more preferably 30-50 parts by weight, based on 100 parts by weight of the inner layer material; And/or, the amount of the second polycaprolactone resin in the outer layer material is 20 to 300 parts by weight, preferably 25 to 150 parts by weight.
  3. 3. The medical thermoplastic polycaprolactone composite according to claim 1 or 2, wherein the weight ratio of the fiber bundles to the first polycaprolactone resin is 0.2-6:1, preferably 0.35-4.5:1, more preferably 1-4:1.
  4. 4. A medical thermoplastic polycaprolactone composite according to any of claims 1-3, wherein the number average molecular weight of the first polycaprolactone resin is 10000-100000g/mol, preferably 15000-80000g/mol, more preferably 20000-80000g/mol, even more preferably 30000-80000g/mol; and/or the number average molecular weight of the second polycaprolactone resin is 40000-150000, preferably 40000-120000g/mol, more preferably 50000-120000g/mol, further preferably 50000-80000g/mol; Preferably, the number average molecular weight of the first polycaprolactone resin is 20000 to 60000g/mol, preferably 20000 to 55000g/mol, and the number average molecular weight of the second polycaprolactone resin is 50000 to 120000g/mol; more preferably, the first polycaprolactone resin has a number average molecular weight of 30000 to 50000g/mol and the second polycaprolactone resin has a number average molecular weight of 60000 to 120000g/mol; Preferably, the first polycaprolactone resin has a number average molecular weight of 30000-80000g/mol, preferably 50000-80000g/mol, and the second polycaprolactone resin has a number average molecular weight of 30000-60000g/mol; more preferably, the first polycaprolactone resin has a number average molecular weight of 60000-80000g/mol and the second polycaprolactone resin has a number average molecular weight of 40000-55000g/mol.
  5. 5. The medical thermoplastic polycaprolactone composite according to any one of claims 1-4, wherein the weight ratio of the second polycaprolactone resin to the first polycaprolactone resin is 0.05-15:1,0.1-15:1, preferably 0.2-10:1, more preferably 0.5-3.5:1; or when the number average molecular weight of the second polycaprolactone resin is 40000-55000, the weight ratio of the second polycaprolactone resin to the first polycaprolactone resin is 0.8-10:1, preferably 1-10:1, more preferably 1-3.5:1.
  6. 6. The medical thermoplastic polycaprolactone composite material of any of claims 1-5, wherein the fiber bundles are selected from at least one of glass fibers, carbon fibers, basalt fibers, aromatic polyamide fibers, stainless steel fibers, synthetic resin fibers, and mineral fibers; And/or the inner layer material consists of fiber bundles, first polycaprolactone resin and first auxiliary agent; and/or the outer layer material is free of fibers. In some preferred embodiments, the outer layer material consists of a second polycaprolactone resin, glass beads, and a second aid.
  7. 7. The medical thermoplastic polycaprolactone composite according to any of claims 1-6, wherein the VOC inhibitor is selected from cage polysilsesquioxane, preferably the cage polysilsesquioxane is selected from octavinyl POSS, octaisobutyl POSS, octaphenyl POSS, octamethyl POSS, and octaisooctyl POSS; and/or, taking the mass of the first polycaprolactone resin and the mass of the second polycaprolactone resin as 100 parts by weight, wherein the amount of the VOC inhibitor in the first auxiliary agent is 0-1.5 parts by weight, and the amount of the VOC inhibitor in the second auxiliary agent is 0.05-1.5 parts by weight.
  8. 8. The medical thermoplastic polycaprolactone composite material of any of claims 1-7, wherein the glass microspheres are hollow glass microspheres; And/or the particle diameter D50 of the glass beads is 10-60 mu m; and/or, the glass beads may be added in an amount of 5 to 30 parts by weight based on 100 parts by weight of the outer layer material; Preferably, the glass beads are hollow glass beads having a particle size D50 of 12-30 μm, preferably 12-25 μm, and/or a wall thickness of 1-3 μm, and/or a true density of 0.2-0.9g/cm 3 .
  9. 9. The medical thermoplastic polycaprolactone composite of any of claims 1-8, wherein the first and second aids further each independently comprise at least one of 0.5-15 parts by weight of a compatibilizer, 0.05-3 parts by weight of an antioxidant, and 0.05-2.5 parts by weight of a lubricant, based on 100 parts by weight of the first and second polycaprolactone resins, respectively; Preferably, the first auxiliary agent and the second auxiliary agent each independently include at least one of 1 to 15 parts by weight, preferably 1 to 6 parts by weight, more preferably 3 to 6 parts by weight of a compatibilizer, 0.1 to 1 part by weight, preferably 0.1 to 0.5 part by weight of an antioxidant, and 0.1 to 2.5 parts by weight, preferably 0.2 to 1 part by weight of a lubricant, based on 100 parts by weight of the first polycaprolactone resin and the second polycaprolactone resin, respectively. And/or the content of the fiber bundles is 10 to 80 wt%, preferably 20 to 70 wt%, more preferably 20 to 50 wt%, based on 100 wt% of the medical thermoplastic polycaprolactone composite material.
  10. 10. The method for preparing a medical thermoplastic polycaprolactone composite material according to any one of claims 1-9, wherein the method for preparing comprises the steps of: Step A, mixing and melting a first polycaprolactone resin and a first auxiliary agent to obtain a first component melt; Step B, carrying out first impregnation treatment on the continuous fiber bundles and the first component melt to form a filiform core layer product; Step C, mixing and melting the second polycaprolactone resin, the glass beads and the second auxiliary agent to obtain a second component melt; And D, carrying out second impregnation treatment on the filiform core layer product and the second component melt to form a resin layer for continuously wrapping the core layer.
  11. 11. Use of the medical thermoplastic polycaprolactone composite material according to any of claims 1-9 in the field of medical surgery.
  12. 12. A medical immobilization material, wherein the medical immobilization material is formed from the medical thermoplastic polycaprolactone composite of any one of claims 1-9.

Description

Medical thermoplastic polycaprolactone composite material and preparation method and application thereof Technical Field The invention belongs to the field of polymer composite materials, and particularly relates to a medical thermoplastic polycaprolactone composite material, and a preparation method and application thereof. Background The polycaprolactone (Polycaprolactone, PCL) is also called as poly epsilon-caprolactone, is a high molecular organic polymer obtained by ring-opening polymerization of epsilon-caprolactone monomer under the catalysis of metal anion complex catalyst, and poly epsilon-caprolactone with different molecular weights can be obtained by controlling polymerization conditions. Polycaprolactone is a white solid powder, is non-toxic and insoluble in water. The PCL has good biocompatibility, good organic polymer compatibility and good biodegradability, can be used as a cell growth support material, can be mutually compatible with various conventional plastics, and can be completely degraded in natural environment for 6-12 months. In addition, PCL has good shape memory temperature control property and is widely applied to medical materials. Currently, medical fixing materials are mainly gypsum, high molecular gypsum, thermoplastic plates and the like. The thermoplastic plate has the advantages of reusability, environmental protection, easy low-temperature forming and the like, and has better application prospect. The melting point of caprolactone used in the thermoplastic plate is about 60-65 ℃, the caprolactone has better mechanical strength below the melting point, and is rapidly softened when being higher than the melting point, and the caprolactone can be continuously kept in a softened state for shaping when the melting point is reduced to about 45 ℃ without causing damage to the skin of a patient, so the caprolactone is very suitable for being used as a medical fixing material. However, PCL softens too quickly above the melting point, and the PCL tends to sag due to gravity for a long period of time, even fails to maintain its shape, and may adhere to itself and fail to use due to improper operation. Polycaprolactone is a typical semi-crystalline polymer with a high shrinkage rate, resulting in excessive shrinkage after cooling and setting, and a high shrinkage force, which is detrimental to patient medical protection. In addition, the strength at normal temperature is suitable for fixing fingers or upper limbs, and is still slightly insufficient for lower limbs or trunk, and a certain gap is formed between the lower limbs or trunk and gypsum. Aiming at the defects of PCL, inorganic fillers such as talcum powder, calcium carbonate and the like are generally adopted for filling modification at home and abroad, the strength of the material can be improved to a certain extent, the cost of the material is reduced, but the compatibility of a large amount of fillers and PCL matrix resin is still to be improved, and the toughness is greatly reduced while the strength is improved. Long fiber reinforced thermoplastic composites are one of the most rapidly growing materials in the composite market today, a common thermoplastic composite. As semi-structural materials and structural materials, long fiber reinforced thermoplastic composites are developed for various fields of industry and civilian use, including fields of automobiles, appliances, entertainment, food processing, communications, electronic appliances, electric tools, gardening, and the like. The fiber length of the long fiber reinforced thermoplastic material is equal to the particle length, the fiber orientation is highly uniform, and the long fiber reinforced thermoplastic material has the characteristics of low density, easiness in molding, high specific strength, high modulus, good fatigue resistance, no water absorption and the like. In addition, the material has the advantages of good dimensional stability, excellent impact resistance, chemical stability (salt resistance, oil resistance, fuel resistance and the like) and recycling, and is particularly suitable for being used in occasions with frequent high-low temperature alternation. The long fiber reinforced thermoplastic material can be injection molded on a common injection molding machine, can also be compression molded, and is an ideal candidate for metal substitute materials. Among them, glass fibers, particularly continuous/fixed length glass fibers, have been used in conventional plastics. Chinese patent application CN114437456a discloses a thermoplastic composite material with a core-shell structure, which can make the performances of the components cooperate, improve the fluidity of the fiber in the resin melt, and expand the application range. However, this patent does not address degradable materials, particularly low temperature materials such as medical polycaprolactone. The medical fixing material which can improve the processing and shaping capacity of the